Carbamates

ABSTRACT

The present invention relates to carbamates of formula (I), 
     
       
         
         
             
             
         
       
         
         wherein the variables are defined according to the description, 
         as well as to a process for manufacturing carbamates of formula (I), and to the use of carbamates of formula (I) in manufacturing benzoxazinones of formula (VII).

The invention relates to carbamates of formula (I), a process formanufacturing the same and their use for manufacturing benzoxazinones.

There is an ongoing need for plant protection compounds, for exampleherbicides, since weeds cause tremendous global economic losses byreducing crop yields and lowering crop quality. Accordingly there isalso a need for efficient and improved manufacturing processes allowingthe preparation of such plant protection compounds, for exampleherbicides.

Surprisingly it has been found that carbamates of formula (I) arepotential intermediates for the preparation of active ingredients, forexample for the preparation of the herbicidal active ingredients asdescribed in WO 10/145992.

Accordingly, the present invention relates carbamates of formula (I),

-   -   wherein    -   R¹ is H or C₁-C₆-alkyl;    -   R² is H or C₁-C₆-alkyl;    -   R³ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-cyanoalkyl,        C₁-C₆-nitroalkyl, aryl, 5- or 6-membered heteroaryl or        aryl-C₁-C₆-alkyl,        -   wherein the aryl or heteroaryl rings are unsubstituted,            partially or fully halogenated, or substituted by one to            five substituents selected from the group consisting of CN,            NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy,            C₁-C₆-haloalkoxy, formyl, C₁-C₆-alkylcarbonyl,            hydroxycarbonyl, and C₁-C₆-alkoxycarbonyl;    -   and    -   Z is O or S.

Further the present invention relates to a process for the preparationof carbamates of formula (I) by reacting (thio)urea compounds of formula(II) with chloroformic acid esters of formula (III) in the presence of abase.

In a further aspect of the present invention there is provided the useof carbamates of formula (I) in manufacturing benzoxazinones of formula(VII).

The organic moieties mentioned in the definition of the compounds andthe substituents according to the invention, esp. of variables R¹ to R³are-like the term halogen-collective terms for individual enumerationsof the individual group members. The term halogen denotes in each casefluorine, chlorine, bromine or iodine. All hydrocarbon chains, i.e. allalkyl, can be straight-chain or branched, the prefix C_(n)-C_(m)denoting in each case the possible number of carbon atoms in the group.

Examples of such meanings are:

-   -   C₁-C₄-alkyl: for example CH₃, C₂H₅, n-propyl, CH(CH₃)₂ n-butyl,        CH(CH₃)—C₂H₅, CH₂—CH(CH₃)₂ and C(CH₃)₃;    -   C₁-C₆-alkyl and also the C₁-C₆-alkyl moieties of        C₃-C₆-cycloalkyl-C₁-C₆-alkyl, C₁-C₆-cyanoalkyl,        C₁-C₆-nitroalkyl, aryl-C₁-C₆-alkyl, C₁-C₆-alkylcarbonyl:        C₁-C₄-alkyl as mentioned above, and also, for example, n-pentyl,        1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,        1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,        1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,        1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,        2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,        1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,        1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or        1-ethyl-2-methylpropyl, preferably methyl, ethyl, n-propyl,        1-methylethyl, n-butyl, 1,1-dimethylethyl, n-pentyl or n-hexyl;    -   C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which        is partially or fully substituted by fluorine, chlorine, bromine        and/or iodine, for example, chloromethyl, dichloromethyl,        trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,        chlorofluoromethyl, dichlorofluoro-methyl, chlorodifluoromethyl,        bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl,        2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,        2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,        2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,        2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl,        3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,        2-chloropropyl, 3-chloropropyl, 2,3-dichloro-propyl,        2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,        3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl,        heptafluoropropyl, a C₁-C₃-haloalkyl radical as mentioned above,        and also, for example, 1-(fluoromethyl)-2-fluoroethyl,        1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,        4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl,        1,1,2,2,-tetrafluoroethyl and        1-trifluoromethyl-1,2,2,2-tetrafluoroethyl;    -   C₁-C₆-haloalkyl: C₁-C₄-haloalkyl as mentioned above, and also,        for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl,        5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl,        6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;    -   C₃-C₆-cycloalkyl and also the cycloalkyl moieties of        C₃-C₆-cycloalkyl-C₁-C₆-alkyl: monocyclic saturated hydrocarbons        having 3 to 6 ring members, such as cyclopropyl, cyclobutyl,        cyclo-pentyl and cyclohexyl;    -   C₃-C₆-alkenyl: for example 1-propenyl, 2-propenyl,        1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,        1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,        2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,        4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,        3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,        3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,        3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,        1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,        1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,        3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,        2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,        1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,        4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,        3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,        2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,        1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,        1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,        1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,        1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,        2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,        2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,        3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,        1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,        2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,        1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,        1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;    -   C₂-C₆-alkenyl: a C₃-C₆-alkenyl radical as mentioned above, and        also ethenyl;    -   C₃-C₆-haloalkenyl: a C₃-C₆-alkenyl radical as mentioned above        which is partially or fully substituted by fluorine, chlorine,        bromine and/or iodine, for example 2-chloroprop-2-en-1-yl,        3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl,        3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloro-2-en-1-yl,        2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl,        3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1-yl,        3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromo-2-en-1-yl or        2,3-dibromobut-2-en-1-yl;    -   C₃-C₆-alkynyl: for example 1-propynyl, 2-propynyl, 1-butynyl,        2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,        2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,        1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,        1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl,        2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,        1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,        2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,        4-methyl-1-pentynyl, 4-methyl-2-pentynyl,        1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl,        1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,        3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,        2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;    -   C₂-C₆-alkynyl: C₃-C₆-alkynyl as mentioned above and also        ethynyl;    -   C₃-C₆-haloalkynyl: C₃-C₆-alkynyl as mentioned above which is        partially or fully substituted by fluorine, chlorine, bromine        and/or iodine, for example 1,1-difluoroprop-2-yn-1-yl,        3-chloroprop-2-yn-1-yl, 3-bromoprop-2-yn-1-yl,        3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl,        4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl,        4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl,        5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or        6-iodohex-5-yn-1-yl;    -   C₁-C₄-alkoxy: for example methoxy, ethoxy, propoxy,        1-methylethoxy butoxy, 1-methylpropoxy, 2-methylpropoxy and        1,1-dimethylethoxy;    -   C₁-C₆-alkoxy and also the C₁-C₆-alkoxy moieties of        C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxycarbonyl: C₁-C₄-alkoxy as        mentioned above, and also, for example, pentoxy, 1-methylbutoxy,        2-methylbutoxy, 3-methoxylbutoxy, 1,1-dimethylpropoxy,        1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy,        hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy,        4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy,        1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy,        3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy,        1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy,        1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;    -   C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above        which is partially or fully substituted by fluorine, chlorine,        bromine and/or iodine, i.e., for example, fluoromethoxy,        difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy,        bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy,        2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy,        2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,        2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,        2,2,2-trichloro-ethoxy, pentafluoroethoxy, 2-fluoropropoxy,        3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy,        2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy,        2,3-difluoropropoxy, 2,3-dichloropropoxy,        3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,        2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,        1-(fluoromethyl)-2-fluoroethoxy,        1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromo-ethoxy,        4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and        nonafluorobutoxy;    -   C₁-C₆-haloalkoxy: C₁-C₄-haloalkoxy as mentioned above, and also,        for example, 5-fluoro-pentoxy, 5-chloropentoxy, 5-bromopentoxy,        5-iodopentoxy, undecafluoropentoxy, 6-fluoro-hexoxy,        6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and        dodecafluorohexoxy;    -   aryl and also the aryl moieties of aryl-C₁-C₆-alkyl: a mono- to        trinuclear aromatic carbocycle having 6 to 14 ring members, such        as for example phenyl, naphthyl, anthracenyl and phenanthrenyl;    -   5- or 6-membered heteroaryl: an aromatic 5- or 6-membered        monocyclic heterocycle which, in addition to carbon atoms        comprises one to three nitrogen atoms, one or two nitrogen atoms        and one sulfur atom, one nitrogen and one oxygen atom, one        oxygen atom, or one sulfur atom as ring members, for example        5-membered aromatic rings such as like furyl (for example        2-furyl, 3-furyl), thienyl (for example 2-thienyl, 3-thienyl),        pyrrolyl (for example pyrrol-2-yl, pyrrol-3-yl), pyrazolyl (for        example pyrazol-3-yl, pyrazol-4-yl), isoxazolyl (for example        isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl), isothiazolyl (for        example isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl),        imidazolyl (for example imidazole-2-yl, imidazole-4-yl),        oxazolyl (for example oxazol-2-yl, oxazol-4-yl, oxazol-5-yl),        thiazolyl (for example thiazol-2-yl, thiazol-4-yl,        thiazol-5-yl), oxadiazolyl (for example 1,2,3-oxadiazol-4-yl,        1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl,        1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl), thiadiazolyl (for        example 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl,        1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl,        1,3,4-thiadiazolyl-2-yl), triazolyl (for example        1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl); and for example        6-membered aromatic rings such as pyridyl (for example        pyridine-2-yl, pyridine-3-yl, pyridine-4-yl), pyrazinyl (for        example pyridazin-3-yl, pyridazin-4-yl), pyrimidinyl (for        example pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl),        pyrazin-2-yl, triazinyl (for example 1,3,5-triazin-2-yl,        1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl).

The preferred embodiments of the invention mentioned herein below haveto be understood as being preferred either independently from each otheror in combination with one another.

According to a preferred embodiment of the invention preference is alsogiven to those carbamates of formula (I), wherein the variables, eitherindependently of one another or in combination with one another, havethe following meanings:

-   R¹ is preferably C₁-C₆-alkyl;    -   more preferably C₁-C₄-alkyl;    -   most preferably CH₃;-   R² is preferably C₁-C₆-alkyl;    -   more preferably C₁-C₄-alkyl;    -   most preferably CH₃;-   R³ is preferably C₁-C₆-alkyl, aryl, 5- or 6-membered heteroaryl or    aryl-C₁-C₆-alkyl, wherein the heteroaryl or aryl ring is    -   unsubstituted, partially or fully halogenated, or substituted by        one to five substituents selected from the group consisting of        CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and        C₁-C₆-haloalkoxy;    -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;    -   also most preferred substituted by one chlorine atom;    -   also most preferred substituted by one CH₃ group;

particularly preferred C₁-C₆-alkyl or aryl, wherein the aryl ring is

-   -   unsubstituted, partially or fully halogenated, or substituted by        one to five substituents selected from the group consisting of        CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and        C₁-C₆-haloalkoxy;    -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;    -   also most preferred substituted by one chlorine atom;    -   also most preferred substituted by one CH₃ group;

also particularly preferred aryl or aryl-C₁-C₆-alkyl, wherein the arylring is

-   -   unsubstituted, partially or fully halogenated, or substituted by        one to five substituents    -   selected from the group consisting of CN, NO₂, C₁-C₆-alkyl,        C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and C₁-C₆-haloalkoxy;    -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;    -   also most preferred substituted by one chlorine atom;    -   also most preferred substituted by one CH₃ group;

also particularly preferred C₁-C₆-alkyl or aryl-C₁-C₆-alkyl, wherein thearyl ring is unsubstituted, partially or fully halogenated, orsubstituted by one to five substituents selected from the groupconsisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxyand C₁-C₆-haloalkoxy;

-   -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;    -   also most preferred substituted by one chlorine atom;    -   also most preferred substituted by one CH₃ group;

especially preferred C₁-C₆-alkyl;

more preferred CH₃;

also especially preferred aryl, wherein the aryl ring is

-   -   unsubstituted, partially or fully halogenated, or substituted by        one to five substituents selected from the group consisting of        CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and        C₁-C₆-haloalkoxy;    -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;

also most preferred substituted by one chlorine atom;

-   -   also most preferred substituted by one CH₃ group;

also especially preferred aryl-C₁-C₆-alkyl, wherein the aryl-C₁-C₆-alkylring is

-   -   unsubstituted, partially or fully halogenated, or substituted by        one to five substituents selected from the group consisting of        CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and        C₁-C₆-haloalkoxy;    -   particularly preferred unsubstituted, partially or fully        halogenated or substituted by one C₁-C₆-alkyl group;    -   especially preferred unsubstituted or substituted by one halogen        atom or one C₁-C₆-alkyl group;    -   more preferred unsubstituted, substituted by one chlorine atom        or by one CH₃ group;    -   most preferred unsubstituted;    -   also most preferred substituted by one chlorine atom;    -   also most preferred substituted by one CH₃ group;

-   R³ is also preferably C₁-C₆-alkyl, phenyl or benzyl,    -   more preferably methyl, ethyl, phenyl or benzyl,    -   especially preferably methyl, phenyl or benzyl,

wherein the phenyl or the benzyl ring is

-   -   unsubstituted, partially or fully halogenated or substituted by        one C₁-C₆-alkyl group, particularly preferred unsubstituted or        substituted by one halogen atom or one C₁-C₆-alkyl group;    -   especially preferred unsubstituted, substituted by one chlorine        atom or by one CH₃ group;

more preferred unsubstituted;

-   -   also more preferred substituted by one chlorine atom,    -   also more preferred substituted by one CH₃ group;

particularly preferred C₁-C₆-alkyl or phenyl, wherein the phenyl ring is

-   -   unsubstituted, partially or fully halogenated or substituted by        one C₁-C₆-alkyl group,    -   particularly preferred unsubstituted or substituted by one        halogen atom or one C₁-C₆-alkyl group;    -   especially preferred unsubstituted, substituted by one chlorine        atom or by one CH₃ group;    -   more preferred unsubstituted;    -   also more preferred substituted by one chlorine atom,    -   also more preferred substituted by one CH₃ group;

also particularly preferred phenyl or benzyl, wherein the phenyl or thebenzyl ring is

-   -   unsubstituted, partially or fully halogenated or substituted by        one C₁-C₆-alkyl group,    -   particularly preferred unsubstituted or substituted by one        halogen atom or one C₁-C₆-alkyl group;    -   especially preferred unsubstituted, substituted by one chlorine        atom or by one CH₃ group;

more preferred unsubstituted;

-   -   also more preferred substituted by one chlorine atom, also more        preferred substituted by one CH₃ group;

also particularly preferred C₁-C₆-alkyl or benzyl, wherein the benzylring is

-   -   unsubstituted, partially or fully halogenated or substituted by        one C₁-C₆-alkyl group,    -   particularly preferred unsubstituted or substituted by one        halogen atom or one C₁-C₆-alkyl group;    -   especially preferred unsubstituted, substituted by one chlorine        atom or by one CH₃ group;    -   more preferred unsubstituted;    -   also more preferred substituted by one chlorine atom,    -   also more preferred substituted by one CH₃ group;

especially preferred phenyl, wherein the phenyl ring is

-   -   unsubstituted, partially or fully halogenated or substituted by        one C₁-C₆-alkyl group,    -   particularly preferred unsubstituted or substituted by one        halogen atom or one C₁-C₆-alkyl group;    -   especially preferred unsubstituted, substituted by one chlorine        atom or by one CH₃ group;    -   more preferred unsubstituted;    -   also more preferred substituted by one chlorine atom,    -   also more preferred substituted by one CH₃ group;

-   Z is preferably O,    -   is also preferably S.

Particular preference is also given to carbamates of formulae (I.1) to(I.8) of Table A listed below, in which the variables R¹, R², R³ and Ztogether have the meanings given in one row of Table A (carbamates offormulae I.1 to I.8); and where the definitions of the variables R¹, R²,R³ and Z are of particular importance for the compounds according to theinvention not only in combination with one another but in each case alsoon their own:

TABLE A No. R¹ R² R³ Z I.1. CH₃ CH₃ CH₃ O I.2. CH₃ CH₃ C₂H₅ O I.3. CH₃CH₃ C₆H₅ O I.4. CH₃ CH₃ CH₂—C₆H₅ O I.5. CH₃ CH₃ CH₃ S I.6. CH₃ CH₃ C₂H₅S I.7. CH₃ CH₃ C₆H₅ S I.8. CH₃ CH₃ CH₂—C₆H₅ S

More particular preference is given to the carbamates of formulae (I.5)and (I.7) as defined above:

Very particular preference is given to the carbamate of formula (I.5) asdefined above. Also very particular preference is given to the carbamateof formula (I.7) as defined above.

Carbamates of formula (I) can be prepared by reacting (thio)ureacompounds of formula (II),

wherein R¹, R² and Z are defined as in formula (I);

with chloroformic acid esters of formula (III)

wherein R³ is defined as in formula (I);

in the presence of a base.

The reaction of the (thio)urea compounds of formula (II) with thechloroformic acid ester of formula (III), in the presence a base isgenerally carried out at a temperature in the range from −10 to 130° C.,preferably in the range from 15 to 110° C., more preferably in the rangefrom 20 to 80° C.

In one embodiment of the process according to the invention, thechloroformic acid esters of formula (III) are used in excess with regardto the (thio)urea compounds of formula (II).

In another embodiment of the process according to the invention, thechloroformic acid esters of formula (III) and the (thio)urea compound offormula (II) are used in equimolar amounts.

In another embodiment of the process according to the invention, the(thio)urea compounds of formula (II) are used in excess with regard tothe chloroformic acid esters of formula (III).

Preferably the molar ratio of the chloroformic acid esters of formula(III) to the (thio)urea compound of formula (II) is in the range from0.9:1 to 1.5:1, preferably from 1.05:1 to 1.15:1, especially preferred1.1:1, more preferred 1.05:1.

The reaction of the (thio)urea compounds of formula (II) with thechloroformic acid ester of formula (III) is carried out in the presenceof a base.

Examples of suitable bases include metal-containing bases andnitrogen-containing bases.

Examples of suitable metal-containing bases are inorganic compounds suchas alkali metal and alkaline earth metal hydroxides, and other metalhydroxides, such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, magnesium hydroxide, calcium hydroxide and aluminumhydroxide; alkali metal and alkaline earth metal oxide, and other metaloxides, such as lithium oxide, sodium oxide, potassium oxide, magnesiumoxide, calcium oxide and magnesium oxide, iron oxide, silver oxide;alkali metal and alkaline earth metal hydrides such as lithium hydride,sodium hydride, potassium hydride and calcium hydride, alkali metalamides such as lithium amide, sodium amide and potassium amide; alkalimetal and alkaline earth metal acetates such as lithium acetate, sodiumacetate, potassium acetate, magnesium acetate, and calcium acetate;alkali metal and alkaline earth metal carbonates such as lithiumcarbonate, sodium carbonate, potassium carbonate, magnesium carbonate,and calcium carbonate, as well as alkali metal hydrogen carbonates(bicarbonates) such as lithium hydrogen carbonate, sodium hydrogencarbonate, potassium hydrogen carbonate; alkali metal and alkaline earthmetal phosphates such as potassium phosphate, calcium phosphate; metalorganic compounds, preferably alkali metal alkyls such as methyllithium, butyl lithium and phenyl lithium, alkyl magnesium halides suchas methyl magnesium chloride and isopropyl magnesium chloride, as wellas alkali metal and alkaline earth metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide,potassium tert-pentoxide and dimethoxymagnesium; and furthermore organicbases, such as tertiary amines such as trimethylamine, triethylamine,diisopropylethylamine and N-methylpiperidine, pyridine, substitutedpyridines such as collidine, lutidine, N-methylmorpholine and4-dimethylaminopyridine and also bicyclic amines.

Examples of suitable nitrogen-containing bases are C₁-C₆-alkylamines,preferably trialkylamines, for example triethylamine, trimethylamine,N-ethyldiisopropylamine; pyridine, lutidine, collidine,4-(dimethylamino)pyridine (DMAP), imidazole,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

Preferred bases are alkali metal and alkaline earth metal carbonates,alkali metal hydrogen carbonates (bicarbonates) and C₁-C₆-alkylamines.

Especially preferred bases are alkali metal and alkaline earth metalcarbonates and alkali metal hydrogen carbonates (bicarbonates).

The term base as used herein also includes mixtures of two or more,preferably two of the above compounds. Particular preference is given tothe use of one base.

The bases are generally employed in equimolar amounts, however they canalso be employed in understochiometric amounts, in excess or, ifappropriate, be used as solvent.

Preferably the bases are used in excess, more preferably the ratio ofthe (thio)urea compound (II) to the base is in the range from 1:2,preferably from 1:1.8, particularly preferred 1:1.1 mole equivalentsbased on the (thio)urea compound of the formula (II).

It may be advantageous to add the base offset over a period of time.

The reaction of the (thio)urea compounds of formula (II) with thechloroformic acid esters of formula (III) and a base is carried out in asolvent. Suitable in principle are all solvents which are capable ofdissolving the (thio)urea compounds of formula (II) and the chloroformicacid esters of formula (III) at least partly and preferably fully underthe reaction conditions.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene; ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF); esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile; ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; as wellas dipolar aprotic solvents such as sulfolane, dimethyl-sulfoxide,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),1,3-dimethyl-2-imidazolidinone (DMI), N,N′-dimethylpropylene urea(DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are ethers, aromatic hydrocarbons, nitriles andesters as defined above. Particularly preferred solvents are THF,toluene, acetonitrile, ethyl acetate and butyl acetate.

The term solvent as used herein also includes mixtures of two or more ofthe above solvents.

For the reaction, the (thio)urea compounds of formula (II), thechloroformic acid esters of formula (III) and the base may be contactedwith one another in any desired manner, i.e. the reactants and the basemay be introduced into the reaction vessel separately, simultaneously orsuccessively and reacted. For example, the (thio)urea compounds offormula (II) and the chloroformic acid esters of formula (III) may beinitially charged in a reaction vessel, if appropriate with the desiredsolvent, and then the desired reaction conditions may be attained.However, it is also possible to introduce the majority or entirety ofthe (thio)urea compounds of formula (II) and subsequently add thechloroformic acid esters of formula (III), if appropriate in a solvent,under reaction conditions, into the reaction vessel.

It might be advantageous, to add the base a little at a time.

In one embodiment of the process according to the invention, thechloroformic acid esters of formula (III) and the base are initiallycharged in a reaction vessel, if appropriate with the desired solvent,and subsequently the (thio)urea compounds of formula (II) are added,more preferably are added a little at a time, into the reaction vessel.

In a preferred embodiment of the process according to the invention, the(thio)urea compounds of formula (II) and the base are initially chargedin a reaction vessel, if appropriate with the desired solvent, andsubsequently the chloroformic acid esters of formula (III) are added,more preferably are added a little at a time, into the reaction vessel.

Such embodiment is particularly preferred in case R³ within thechloroformic acid esters of formula (III) is C₁-C₆-alkyl, especiallypreferred methyl.

In a further preferred embodiment of the invention, the majority, inparticular at least 80% and more preferably the entirety or virtuallythe entirety (>95%) of the (thio)urea compounds of formula (II) and thebase are initially charged, and the majority, in particular at least 80%and more preferably the entirety or virtually the entirety (>95%) of thechloroformic acid esters of formula (III) is added thereto underreaction conditions in the course of the reaction, for example over aperiod from 0.5 to 20 h and in particular from 1 to 10 h. To this end,the chloroformic acid esters of formula (III) will preferably bedissolved in a solvent.

In another preferred embodiment of the process according to theinvention, the (thio)urea compounds of formula (II) and the chloroformicacid esters of formula (III) are initially charged in a reaction vessel,if appropriate with the desired solvent, and subsequently the base isadded into the reaction vessel; more preferably is added into thereaction vessel a little at a time.

Such embodiment is particularly preferred in case R³ within thechloroformic acid esters of formula (III) is aryl, especially preferredphenyl.

In a further preferred embodiment of the invention, the (thio)ureacompounds of formula (II) and the chloroformic acid esters of formula(III) are initially charged and then the majority, in particular atleast 80% and more preferably the entirety or virtually the entirety(>95%), of the base is added thereto. The reaction may if appropriate becompleted by metering in further base.

The reaction can be carried out at atmospheric pressure, reducedpressure or under elevated pressure, if appropriate under an inert gas,continuously or batchwise.

After completion or partial completion of the reaction, the reactionmixture can be worked up by the methods customary for the purpose bymeans of standard techniques. Examples thereof include filtration,aqueous work-up, and evaporation of solvents and/or other volatilecompounds. These methods can also be combined with each other.

In general the solvent used is removed by customary methods,distillatively for example. The crude product can then be taken up in anon-water-miscible organic solvent, any impurities extracted withunacidified or acidified water, and the system can then be dried and thesolvent removed under reduced pressure.

For further purification it is possible to employ the typical methodssuch as crystallization, precipitation (for example by addition of anapolar solvent such as pentane, cyclohexane, heptane or toluene, ormixtures of said solvents) or chromatography.

The (thio)urea compounds of formula (II) necessary for the preparationof the carbamates of formula (I) are commercially available or can beprepared by methods known in the art.

(Thio)urea compounds of formula (II) can be prepared by reactingiso(thio)cyanates of formula

(IV) with amines of formula (V):

wherein R¹, R² and Z are as defined as in formula (I) above.

The reaction of iso(thio)cyanates of formula (IV) with amines of formula(V) is usually carried out at a temperature in the range from −10 to130° C., preferably in the range from 15 to 110° C., more preferably inthe range from 20 to 40° C. (e.g. G. Kaupp et al., Tetrahedron 56, 2000,pages 6899-6911).

The reaction of the iso(thio)cyanates of formula (IV) with amines offormula (V) is carried out in a solvent.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene; ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF); esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile; ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; as wellas dipolar aprotic solvents such as sulfolane, dimethyl-sulfoxide,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),1,3-dimethyl-2-imidazolidinone (DMI), N,N′-dimethylpropylene urea(DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are ethers, aromatic hydrocarbons, nitriles andesters as defined above. Particularly preferred solvents are THF,acetonitrile and ethyl acetate.

The term solvent as used herein also includes mixtures of two or more ofthe above solvents.

Work up can be carried out in a known manner.

The iso(thio)cyanates of formula (IV) required for the preparation ofthe (thio)urea compounds of formula (II) are commercially available.

The amines of formula (V) required for the preparation of the (thio)ureacompounds of formula (II) are commercially available.

Accordingly, in a further preferred embodiment of the process of theinvention carbamates of formula (I), are prepared by

-   a) reacting iso(thio)cyanates of formula (IV) with amines of    formula (V) to give (thio)urea compounds of formula (II); and-   b) reacting the (thio)urea compounds of formula (II) with    chloroformic acid esters of formula (III) to give carbamates of    formula (I):

In one embodiment of the present invention the (thio)urea compounds offormula (II) are isolated prior to be used in step b), wherein the(thio)urea compounds of formula (II) are reacted with chloroformic acidesters of formula (III) to give carbamates of formula (I) as describedabove.

In another embodiment the (thio)urea compounds of formula (II) are notisolated, and the reaction mixture obtained in step a) is directly usedin step b) and reacted with chloroformic acid esters of formula (III) togive carbamates of formula (I) as described above.

Accordingly, in a further preferred embodiment of the process of theinvention carbamates of formula (I), are prepared by

-   a) reacting iso(thio)cyanates of formula (IV) with amines of formula    (V); and-   b) reacting the reaction mixture resulting from step a) with    chloroformic acid esters of formula (III) to give carbamates of    formula (I).

The chloroformic acid esters of formula (III) necessary for thepreparation of the carbamates of formula (II) are commerciallyavailable.

The carbamates of formula (I) are useful in the synthesis ofbenzoxazinones of formula (VII), which are herbicidal active ingredientsas described in WO 10/145992.

Benzoxazinones of formula (VII) can be prepared by reacting carbamatesof formula (I) with carbamat-benzoxazinones of formula (VI) in thepresence of a base:

wherein

-   -   R¹, R², R³ and Z have the meanings, preferably the preferred        meanings, as defined in formula (I) above;    -   R⁴ is H, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl,        C₃-C₆-alkenyl, C₃-C₆-haloalkenyl, C₃-C₆-alkynyl,        C₃-C₆-haloalkynyl, C₁-C₆-alkoxy or C₃-C₆-cycloalkyl-C₁-C₆-alkyl;    -   R⁵ is H, halogen or C₁-C₆-alkyl;    -   R⁶ is H, halogen or C₁-C₆-alkyl;    -   R⁷ is H, halogen or C₁-C₆-alkyl; and    -   R⁸ is C₁-C₆-haloalkyl, C₁-C₆-cyanoalkyl, C₁-C₆-nitroalkyl, aryl,        5- or 6-membered heteroaryl or aryl-C₁-C₆-alkyl,        -   wherein the aryl or heteroaryl rings are unsubstituted,            partially or fully halogenated, or substituted by one to            five substituents selected from the group consisting of CN,            NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy,            C₁-C₆-haloalkoxy, formyl, C₁-C₆-alkylcarbonyl,            hydroxycarbonyl, and C₁-C₆-alkoxycarbonyl;        -   and    -   W is O or S.

Accordingly, in a further preferred embodiment of the invention thecarbamates of formula (I) are used for the manufacturing ofbenzoxazinones of formula (VII) by reacting the carbamates of formula(I) with carbamat-benzoxazinones of formula (VI) to give benzoxazinonesof formula (VII).

With respect to the substituents within the benzoxazinones of formula(VII),

the particularly preferred embodiments of the benzoxazinones of formula(VII) correspond, either independently of one another or in combinationwith one another, to those of the substituents of R¹, R² and Z offormula (I); and

-   R⁴ is preferably C₃-C₆-alkynyl or C₃-C₆-haloalkynyl, more preferably    C₃-alkynyl or C₃-haloalkynyl, particularly preferred CH₂C≡CH,    CH₂C≡CCl or CH₂C≡CBr;    -   is also preferably C₃-C₆-alkynyl or        C₃-C₆-cycloalkyl-C₁-C₆-alkyl, particularly preferred propargyl        or cyclopropylmethyl;

is also preferably C₃-C₆-alkynyl, more preferably C₃-alkynyl;particularly preferred CH₂C≡CH;

is also preferably C₃-C₆-halolkynyl, more preferably C₃-halolkynyl,particularly preferred CH₂C≡CCl or CH₂C≡CBr;

-   R⁵ is preferably halogen; particularly preferred Cl or F; especially    preferred F;-   R⁶ is preferably H, Cl or F; particularly preferred H or F,    especially preferred H; is also preferably halogen, particularly    preferred F or Cl, especially preferred F;-   R⁷ is preferably H or F; particularly preferred H;    -   is also preferably halogen; particularly preferred F or Cl;        especially preferred F;-   W is preferably O,    -   is also preferably S.

Particular preference is also given to the preparation of benzoxazinonesof formula (VII.a), which correspond to benzoxazinones of formula (VII)wherein R⁵ is F, R¹ and R¹ are CH₃, W is O and Z is S:

wherein the variables R⁴, R⁶ and R⁷ have the meanings, in particular thepreferred meanings, as defined above;

most preference to the preparation of benzoxazinones of formulae(VII.a.1) to (VII.a.54) of Table B listed below, in which the variablesR⁴, R⁶ and R⁷ together have the meanings given in one row of Table A(benzoxazinones of formulae VII.a.1 to VII.a.54); and where thedefinitions of the variables R⁴, R⁶ and R⁷ are of particular importancefor the process and the compounds according to the invention not only incombination with one another but in each case also on their own:

TABLE B No. R⁴ R⁶ R⁷ VII.a.1 H H H VII.a.2 CH₃ H H VII.a.3 C₂H₅ H HVII.a.4 CH₂—C₂H₅ H H VII.a.5 CH(CH₃)₂ H H VII.a.6 CH₂—CH₂—(CH₃)₂ H HVII.a.7 CH₂—CH═CH₂ H H VII.a.8 CH₂C≡CH H H VII.a.9 CH₂C≡C—Br H HVII.a.10 H F H VII.a.11 CH₃ F H VII.a.12 C₂H₅ F H VII.a.13 CH₂—C₂H₅ F HVII.a.14 CH(CH₃)₂ F H VII.a.15 CH₂—CH₂—(CH₃)₂ F H VII.a.16 CH₂—CH═CH₂ FH VII.a.17 CH₂C≡CH F H VII.a.18 CH₂C≡C—Br F H VII.a.19 H H F VII.a.20CH₃ H F VII.a.21 C₂H₅ H F VII.a.22 CH₂—C₂H₅ H F VII.a.23 CH(CH₃)₂ H FVII.a.24 CH₂—CH₂—(CH₃)₂ H F VII.a.25 CH₂—CH═CH₂ H F VII.a.26 CH₂C≡CH H FVII.a.27 CH₂C≡C—Br H F VII.a.28 H F F VII.a.29 CH₃ F F VII.a.30 C₂H₅ F FVII.a.31 CH₂—C₂H₅ F F VII.a.32 CH(CH₃)₂ F F VII.a.33 CH₂—CH₂—(CH₃)₂ F FVII.a.34 CH₂—CH═CH₂ F F VII.a.35 CH₂C≡CH F F VII.a.36 CH₂C≡C—Br F FVII.a.37 H H Cl VII.a.38 CH₃ H Cl VII.a.39 C₂H₅ H Cl VII.a.40 CH₂—C₂H₅ HCl VII.a.41 CH(CH₃)₂ H Cl VII.a.42 CH₂—CH₂—(CH₃)₂ H Cl VII.a.43CH₂—CH═CH₂ H Cl VII.a.44 CH₂C≡CH H Cl VII.a.45 CH₂C≡C—Br H Cl VII.a.46 HF Cl VII.a.47 CH₃ F Cl VII.a.48 C₂H₅ F Cl VII.a.49 CH₂—C₂H₅ F ClVII.a.50 CH(CH₃)₂ F Cl VII.a.51 CH₂—CH₂—(CH₃)₂ F Cl VII.a.52 CH₂—CH═CH₂F Cl VII.a.53 CH₂C≡CH F Cl VII.a.54 CH₂C≡C—Br F Cl

More particular preference is given to the preparation of thebenzoxazinones of formulae (VII.a.28) and (VII.a.35) as defined above:

Very particular preference is given to the preparation of thebenzoxazinone of formula (VII.a.28) as defined above.

Also very particular preference is given to the preparation of thebenzoxazinone of formula (VII.a.35) as defined above.

The reaction of the carbamates of formula (I) with thecarbamat-benzoxazinones of formula (VI) in the presence of a base isgenerally carried out at a temperature in the range from −20° C. to theboiling point of the solvent used; preferably in the range from −20 to150° C., particularly preferred in the range from 0 to 120° C., morepreferably in the range from 20 to 80° C.

In one embodiment of the process according to the invention, thecarbamates of formula (I) and the carbamat-benzoxazinones of formula(VI) are used in equimolar amounts.

In another embodiment of the process according to the invention, thecarbamat-benzoxazinones of formula (VI) are used in excess with regardto the carbamates of formula (I).

In another embodiment of the process according to the invention, thecarbamates of formula (I) are used in excess with regard to thecarbamat-benzoxazinones of formula (VI). This embodiment is preferred.

Preferably the molar ratio of the carbamates of formula (I) to thecarbamat-benzoxazinones of formula (VI) is in the range from 1.5:1 to1:0.9, preferably 1.1:1 to 1:0.9, especially preferred 1:0.9, alsoespecially preferred 1:1.

The reaction of the carbamates of formula (I) with thecarbamat-benzoxazinones of formula (VI) is carried out in the presenceof a base.

Examples of suitable bases include metal-containing bases andnitrogen-containing bases.

Examples of suitable metal-containing bases are inorganic compounds suchas alkali metal and alkaline earth metal hydroxides, and other metalhydroxides, such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, magnesium hydroxide, calcium hydroxide and aluminumhydroxide; alkali metal and alkaline earth metal oxide, and other metaloxides, such as lithium oxide, sodium oxide, potassium oxide, magnesiumoxide, calcium oxide and magnesium oxide, iron oxide, silver oxide;alkali metal and alkaline earth metal hydrides such as lithium hydride,sodium hydride, potassium hydride and calcium hydride; alkali metal andalkaline earth metal formates, acetates and other metal salts ofcarboxylic acids, such as sodium formate, sodium benzoate, lithiumacetate, sodium acetate, potassium acetate, magnesium acetate, andcalcium acetate; alkali metal and alkaline earth metal carbonates suchas lithium carbonate, sodium carbonate, potassium carbonate, magnesiumcarbonate, and calcium carbonate, as well as alkali metal hydrogencarbonates (bicarbonates) such as lithium hydrogen carbonate, sodiumhydrogen carbonate, potassium hydrogen carbonate; alkali metal andalkaline earth metal phosphates such as sodium phosphate, potassiumphosphate and calcium phosphate; alkali metal and alkaline earth metalaryloxides such as sodium phenolate and potassium phenolate; andfurthermore organic bases, such as ammonia, tertiary amines likeC₁-C₆-alkylamines, preferably trialkylamines, such as trimethylamine,triethylamine, diisopropylethylamine, N-ethyldiisopropylamine; and alsoN-methylpiperidine, 4-(dimethylamino)pyridine (DMAP), imidazole,pyridine, substituted pyridines such as collidine, lutidine,N-methylmorpholine and 4-dimethylaminopyridine and also bicyclic amines,such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or1,5-diazabicyclo[4.3.0]non-5-ene (DBN)

Preferred bases are alkali metal and alkaline earth metal aryloxides,alkali metal and alkaline earth metal carbonates and alkali metal andalkaline earth metal acetates as defined above.

Especially preferred bases are alkali metal and alkaline earth metalaryloxides, and alkali metal and alkaline earth metal acetates asdefined above.

The term base as used herein also includes mixtures of two or more,preferably two of the above compounds. Particular preference is given tothe use of one base.

The bases are generally employed in catalytic amounts based on thecarbamat-benzoxazinones of formula (VI), however they can also beemployed in equimolar amounts or in excess.

Preferably the amount of base is from 1.5 mole equivalents to catalyticamounts, more preferably from 0.3 to 0.01 mole equivalents, especiallypreferred from 0.3 to 0.1 mole equivalents based on thecarbamat-benzoxazinones of formula (VI).

The reaction of the carbamates of formula (I) with thecarbamat-benzoxazinones of formula (VI) and a base is usually carriedout in a solvent. However the reaction in melt is possible in principleas well.

Suitable in principle are all solvents which are capable of dissolvingthe carbamates of formula (I) and the carbamat-benzoxazinones of formula(VI) at least partly and preferably fully under reaction conditions.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes, aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene, halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene, ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF), esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile, ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; dipolaraprotic solvents such as sulfolane, N,N-dimethylformamide (DMF),N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone (DMI),N,N′-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO) and1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are esters and dipolar aprotic solvents as describedabove.

More preferred solvents are ethyl acetate and DMF.

The term solvent as used herein also includes mixtures of two or more ofthe above compounds.

For the reaction, the carbamates of formula (I), thecarbamates-benzoxazinones of formula (VI) and the base may be contactedwith one another in any desired manner, i.e. the reactants and the basemay be introduced into the reaction vessel separately, simultaneously orsuccessively and reacted.

For example, the carbamates of formula (I) and thecarbamates-benzoxazinones of formula (VI) may be initially charged in areaction vessel, if appropriate with the desired solvent, and then thedesired reaction conditions may be attained. However, it is alsopossible to introduce the majority or entirety of the carbamates offormula (I) and subsequently add the carbamates-benzoxazinones offormula (VI), if appropriate in a solvent, under reaction conditions,into the reaction vessel.

It might be advantageous, to add the base a little at a time.

In one embodiment of the process according to the invention, thecarbamat-benzoxazinones of formula (VI) and the base are initiallycharged in a reaction vessel, if appropriate with the desired solvent,and subsequently the carbamates of formula (I) are added into thereaction vessel.

In a preferred embodiment of the process according to the invention, thecarbamates of formula (I) and the base are initially charged in areaction vessel, if appropriate with the desired solvent, andsubsequently the carbamat-benzoxazinones of formula (VI) are added intothe reaction vessel.

In a further particular embodiment of the process according to theinvention, in case R³ within the carbamate of formula (I) isC₁-C₆-alkyl, especially preferred methyl, the carbamates of formula (I)and the base are initially charged in a reaction vessel, if appropriatewith the desired solvent, and subsequently the carbamat-benzoxazinonesof formula (VI) are added, more preferably are added a little at a time,into the reaction vessel.

In a further preferred embodiment of the invention, the majority, inparticular at least 80% and more preferably the entirety or virtuallythe entirety (>95%) of the carbamates of formula (I) and the base areinitially charged, and the majority, in particular at least 80% and morepreferably the entirety or virtually the entirety (>95%) of thecarbamat-benzoxazinones of formula (VI) is added thereto under reactionconditions in the course of the reaction, for example over a period from0.5 to 20 h and in particular from 1 to 10 h. To this end, thecarbamat-benzoxazinones of formula (III) will preferably be dissolved ina solvent.

In another preferred embodiment of the process according to theinvention, the carbamates of formula (I) and the carbamat-benzoxazinonesof formula (VI) are initially charged in a reaction vessel, ifappropriate with the desired solvent, and subsequently the base is addedinto the reaction vessel.

The reaction temperature within such preferred embodiment is preferablyin the range from 0 to 120° C., more preferably in the range from 20 to80° C.

Such embodiment is particularly preferred in case R³ within thecarbamate of formula (I) is aryl, especially preferred phenyl.

In a further preferred embodiment of the invention, the carbamates offormula (I) and the carbamates-benzoxazinones of formula (VI) areinitially charged and then the majority, in particular at least 80% andmore preferably the entirety or virtually the entirety (>95%), of thebase is added thereto. The reaction may if appropriate be completed bymetering in further base.

The reaction can be carried out at atmospheric pressure, reducedpressure or under elevated pressure, if appropriate under an inert gas,continuously or batchwise.

Preference is given to partly or completely removing the compound R³O—Hformed in the course of the reaction of the carbamates of formula (I)with carbamat-benzoxazinones of formula (VI), especially when thecompound R³O—H is a C₁-C₄-alkanol such as methanol or ethanol. To thisend, the reaction will be carried out in a manner known per se at atemperature and a pressure at which the compounds R³O—H, if appropriate,are partly or completely distilled out of the reaction mixture,optionally as an azeotrope with the solvent.

If appropriate, fresh solvent can be introduced into the mixture forcompensation or the solvent distilled off with the compounds R³O—H canbe recycled into the reaction after optional distillative depletion ofthe compounds R³O—H.

For these reasons, it is advantageous when the solvent used has aboiling point of at least 10° C., in particular at least 30° C., abovethe boiling point of the compounds R³O—H formed in the reaction (each atatmospheric pressure).

Appropriately, the reaction of the carbamates of formula (I) withcarbamat-benzoxazinones of formula (VI) is carried out in an apparatuswhich is equipped with at least one distillation or rectificationapparatus, for example a distillation column, which firstly allows thecompound R³O—H, if appropriate together with the solvent, to bedistilled off and simultaneously enables removal and recycling of anysolvent distilled off with the compound R³O—H.

After completion or partial completion of the reaction, the reactionmixture can be worked up by the methods customary for the purpose bymeans of standard techniques. Examples thereof include filtration,aqueous work-up, and evaporation of solvents and/or other volatilecompounds. These methods can also be combined with each other.

In general the solvent used is removed by customary methods,distillatively for example. The crude product can then be taken up in anon-water-miscible organic solvent, any impurities extracted withunacidified or acidified water, and the system can then be dried and thesolvent removed under reduced pressure.

For further purification it is possible to employ the typical methodssuch as crystallization, precipitation (for example by addition of anapolar solvent such as pentane, cyclohexane, heptane or toluene, ormixtures of said solvents) or chromatography.

In a preferred embodiment of the reaction, in case the reaction has beencarried out in DMF, the reaction mixture will generally be concentratedand/or cooled and/or a precipitant will be added. Suitable precipitantsare solvents in which the benzoxazinones of formula (I) dissolve only toa slight extent, if at all, at least at temperatures below 25° C.

These include in particular alcohols such as methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, tert.-butanol, water,and the like; or mixtures thereof;

preferably methanol, isobutanol and water, or mixtures thereof.

The precipitation or crystallization may be followed by furtherpurification measures.

In another variant of the reaction in the process according to theinvention and depending on the base used, after the ending of thereaction, it might be advantageous to dilute the reaction mixture byaddition of water and/or acids, the pH of the aqueous phase beingadjusted to pH in between 6 to 8, preferably pH=7.

Acids suitable for this purpose are organic acids and aqueous mineralacids known to the skilled worker, such as acetic acid, hydrochloricacid, sulfuric acid, nitric acid or phosphoric acid, for example.

The reaction mixture can then be worked up by the methods customarytherefor. In general, the phases are separated and the solvent used willbe removed by customary processes, for example by distillation. Forfurther purification, the customary processes such as for examplecrystallization (for example also by addition of a nonpolar solvent suchas pentane, cyclohexane, heptane or toluene, or mixtures of the solventsmentioned) can be employed.

With respect to the substituents within the carbamat-benzoxazinones offormula (VI),

necessary for the use of the carbamates of formula (I) to prepare ofbenzoxazinones of formula (VII) according to the invention, theparticularly preferred embodiments of the carbamat-benzoxazinones offormula (VI) correspond, either independently of one another or incombination with one another, to those of the variables of R⁴, R⁵, R⁶,R⁷ and W of the benzoxazinones of formula (VII), and

-   R⁸ is preferably C₁-C₆-haloalkyl, aryl, or aryl-C₁-C₆-alkyl,    -   wherein the aryl ring is        -   unsubstituted, partially or fully halogenated, or            substituted by one to five substituents selected from the            group consisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,            OH, C₁-C₆-alkoxy and C₁-C₆-haloalkoxy;        -   particularly preferred unsubstituted, partially or fully            halogenated or substituted by one C₁-C₆-alkyl group;        -   especially preferred unsubstituted or substituted by one            halogen atom or one    -   C₁-C₆-alkyl group;        -   more preferred unsubstituted, substituted by one chlorine            atom or by one CH₃ group;        -   most preferred unsubstituted;        -   also most preferred substituted by one chlorine atom;        -   also most preferred substituted by one CH₃ group;    -   particularly preferred C₁-C₆-haloalkyl or aryl,    -   wherein the aryl ring is        -   unsubstituted, partially or fully halogenated, or            substituted by one to five substituents selected from the            group consisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,            OH, C₁-C₆-alkoxy and C₁-C₆-haloalkoxy;        -   particularly preferred unsubstituted, partially or fully            halogenated or substituted by one C₁-C₆-alkyl group;        -   especially preferred unsubstituted or substituted by one            halogen atom or one C₁-C₆-alkyl group;        -   more preferred unsubstituted, substituted by one chlorine            atom or by one CH₃ group;        -   most preferred unsubstituted;        -   also most preferred substituted by one chlorine atom;        -   also most preferred substituted by one CH₃ group;    -   especially preferred C₁-C₆-haloalkyl;    -   also especially preferred aryl, wherein the aryl ring is        -   unsubstituted, partially or fully halogenated, or            substituted by one to five substituents selected from the            group consisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,            OH, C₁-C₆-alkoxy and C₁-C₆-haloalkoxy;        -   particularly preferred unsubstituted, partially or fully            halogenated or substituted by one C₁-C₆-alkyl group;        -   especially preferred unsubstituted or substituted by one            halogen atom or one C₁-C₆-alkyl group;        -   more preferred unsubstituted, substituted by one chlorine            atom or by one CH₃ group;        -   most preferred unsubstituted;        -   also most preferred substituted by one chlorine atom;        -   also most preferred substituted by one CH₃ group;    -   more preferred phenyl, wherein the phenyl ring is        -   unsubstituted, partially or fully halogenated, or            substituted by one to five substituents selected from the            group consisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,            OH, C₁-C₆-alkoxy and C₁-C₆-haloalkoxy;        -   particularly preferred unsubstituted, partially or fully            halogenated or substituted by one C₁-C₆-alkyl group;        -   especially preferred unsubstituted or substituted by one            halogen atom or one C₁-C₆-alkyl group;        -   more preferred unsubstituted, substituted by one chlorine            atom or by one CH₃ group;        -   most preferred unsubstituted;        -   also most preferred substituted by one chlorine atom;        -   also most preferred substituted by one CH₃ group;    -   also more preferred phenyl, wherein the phenyl ring is        -   partially or fully halogenated, or substituted by one to            five substituents selected from the group consisting of CN,            NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy and            C₁-C₆-haloalkoxy;        -   particularly preferred partially or fully halogenated or            substituted by one C₁-C₆-alkyl group;        -   especially preferred substituted by one halogen atom or one            C₁-C₆-alkyl group;        -   more preferred substituted by one chlorine atom or by one            CH₃ group.

Particular preference is given to the carbamat-benzoxazinones of formula(VI.a), which correspond to carbamat-benzoxazinones of formula (VI)wherein R⁵ is F, R⁸ is phenyl and W is O:

wherein the variables R⁴, R⁶ and R⁷ have the meanings, in particular thepreferred meanings, as defined above;

special preference is given to the carbamat-benzoxazinones of formulae(VI.a.1) to (VI.a.54) of Table C listed below, in which the variablesR⁴, R⁶ and R⁷ together have the meanings given in one row of Table C(carbamat-benzoxazinones of formulae VI.a.1 to VI.a.54); and where thedefinitions of the variables R⁴, R⁶ and R⁷ are of particular importancefor the process according to the invention not only in combination withone another but in each case also on their own:

TABLE C No. R⁴ R⁷ R⁶ VI.a.1 H H H VI.a.2 CH₃ H H VI.a.3 C₂H₅ H H VI.a.4CH₂—C₂H₅ H H VI.a.5 CH(CH₃)₂ H H VI.a.6 CH₂—CH₂—(CH₃)₂ H H VI.a.7CH₂—CH═CH₂ H H VI.a.8 CH₂C≡CH H H VI.a.9 CH₂C≡C—Br H H VI.a.10 H H FVI.a.11 CH₃ H F VI.a.12 C₂H₅ H F VI.a.13 CH₂—C₂H₅ H F VI.a.14 CH(CH₃)₂ HF VI.a.15 CH₂—CH₂—(CH₃)₂ H F VI.a.16 CH₂—CH═CH₂ H F VI.a.17 CH₂C≡CH H FVI.a.18 CH₂C≡C—Br H F VI.a.19 H F H VI.a.20 CH₃ F H VI.a.21 C₂H₅ F HVI.a.22 CH₂—C₂H₅ F H VI.a.23 CH(CH₃)₂ F H VI.a.24 CH₂—CH₂—(CH₃)₂ F HVI.a.25 CH₂—CH═CH₂ F H VI.a.26 CH₂C≡CH F H VI.a.27 CH₂C≡C—Br F H VI.a.28H F F VI.a.29 CH₃ F F VI.a.30 C₂H₅ F F VI.a.31 CH₂—C₂H₅ F F VI.a.32CH(CH₃)₂ F F VI.a.33 CH₂—CH₂—(CH₃)₂ F F VI.a.34 CH₂—CH═CH₂ F F VI.a.35CH₂C≡CH F F VI.a.36 CH₂C≡C—Br F F VI.a.37 H Cl H VI.a.38 CH₃ Cl HVI.a.39 C₂H₅ Cl H VI.a.40 CH₂—C₂H₅ Cl H VI.a.41 CH(CH₃)₂ Cl H VI.a.42CH₂—CH₂—(CH₃)₂ Cl H VI.a.43 CH₂—CH═CH₂ Cl H VI.a.44 CH₂C≡CH Cl H VI.a.45CH₂C≡C—Br Cl H VI.a.46 H Cl F VI.a.47 CH₃ Cl F VI.a.48 C₂H₅ Cl F VI.a.49CH₂—C₂H₅ Cl F VI.a.50 CH(CH₃)₂ Cl F VI.a.51 CH₂—CH₂—(CH₃)₂ Cl F VI.a.52CH₂—CH═CH₂ Cl F VI.a.53 CH₂C≡CH Cl F VI.a.54 CH₂C≡C—Br Cl F

Also particularly preferred are the carbamat-benzoxazinones of formulaVI.b, particularly preferred the carbamat-benzoxazinones of formulaeVI.b.1 to VI.b.54, which differ from the correspondingcarbamat-benzoxazinones of formulae VI.a.1 to VI.a.54 only in that R⁸ is4-chloro-phenyl:

Also particularly preferred are the carbamat-benzoxazinones of formulaVI.c, particularly preferred the carbamat-benzoxazinones of formulaeVI.c.1 to VI.c.54, which differ from the correspondingcarbamat-benzoxazinones of formulae VI.a.1 to VI.a.54 only in that R⁸ is4-CH₃-phenyl:

Also particularly preferred are the carbamat-benzoxazinones of formulaVI.d, particularly preferred the carbamat-benzoxazinones of formulaeVI.d.1 to VI.d.54, which differ from the correspondingcarbamat-benzoxazinones of formulae VI.a.1 to VI.a.54 only in that R⁸ is3-CH₃-phenyl:

Also particularly preferred are the carbamat-benzoxazinones of formulaVI.e, particularly preferred the carbamat-benzoxazinones of formulaeVI.e.1 to VI.e.54, which differ from the correspondingcarbamat-benzoxazinones of formulae VI.a.1 to VI.a.54 only in that R⁸ is2-CH₃-phenyl:

More particular preference is given to the carbamat-benzoxazinones offormulae (VI.a.28) and (VI.a.35), as defined above:

Very particular preference is given to the carbamat-benzoxazinone offormula (VI.a.28). Also very particular preference is given to thecarbamat-benzoxazinone of formula (IVI.a.35).

The carbamat-benzoxazinones of formula (VI) necessary for the use of thecarbamates of formula (I) to prepare of benzoxazinones of formula (VII)can be prepared by reacting amino-benzoxazinones of formula (VIII) withcompounds of formula (IX), optionally in the presence of a base:

In case the reaction of the amino-benzoxazinones of formula (VIII) withcompounds of formula (IX), is conducted in the presence of a base, thereaction is generally carried out at a temperature in the range from−40° C. to the boiling point of the solvent used, for example from −40to 150° C., preferably in the range from −20 to 100° C., more preferablyin the range from 0 to 70° C.

In case the reaction of the amino-benzoxazinones of formula (VIII) withcompounds of formula (IX), is conducted in the absence of a base, thereaction is generally carried out at a temperature in the range from−40° C. to the boiling point of the solvent used, for example from −40to 150° C., preferably in the range from 0 to 150° C., more preferablyin the range from 50 to 130° C.

In case THF is used as the solvent, the reaction is preferably carriedout at room temperature, i.e. at about 20° C.

In one embodiment of the process according to the invention, thecompounds of formula (IX) are used in excess with regard to theamino-benzoxazinones of formula (VIII).

In another embodiment of the process according to the invention, thecompounds of formula (IX) and the amino-benzoxazinones of formula (VIII)are used in equimolar amounts.

In another embodiment of the process according to the invention, theamino-benzoxazinones of formula (VIII) are used in excess with regard tothe compounds of formula (IX).

Preferably the molar ratio of the compounds of formula (IX) to theamino-benzoxazinones of formula (VIII) is in the range from 0.9:1 to1.5:1, preferably from 1.0:1 to 1.1.:1.

In one embodiment the reaction of the amino-benzoxazinone of formula(VIII) with the compounds of formula (IX) is carried out in the presenceof a base.

Examples of suitable bases include metal-containing bases andnitrogen-containing bases. Examples of suitable metal-containing basesare inorganic compounds such as alkali metal and alkaline earth metalhydroxides, and other metal hydroxides, such as lithium hydroxide,sodium hydroxide, potassium hydroxide, magnesium hydroxide, calciumhydroxide and aluminum hydroxide; alkali metal and alkaline earth metaloxide, and other metal oxides, such as lithium oxide, sodium oxide,potassium oxide, magnesium oxide, calcium oxide and magnesium oxide,iron oxide, silver oxide; alkali metal and alkaline earth metal hydridessuch as lithium hydride, sodium hydride, potassium hydride and calciumhydride; alkali metal and alkaline earth metal acetates such as lithiumacetate, sodium acetate, potassium acetate, magnesium acetate, andcalcium acetate; alkali metal and alkaline earth metal carbonates suchas lithium carbonate, sodium carbonate, potassium carbonate, magnesiumcarbonate, and calcium carbonate, as well as alkali metal hydrogencarbonates (bicarbonates) such as lithium hydrogen carbonate, sodiumhydrogen carbonate, potassium hydrogen carbonate; alkali metal andalkaline earth metal phosphates such as potassium phosphate, calciumphosphate; metal organic compounds, preferably alkali metal alkyls suchas methyl lithium, butyl lithium and phenyl lithium; alkyl magnesiumhalides such as methyl magnesium chloride and isopropyl magnesiumchloride as well as alkali metal and alkaline earth metal alkoxides suchas sodium methoxide, sodium ethoxide, potassium ethoxide, potassiumtert-butoxide, potassium tert-pentoxide and dimethoxymagnesium.

Examples of suitable nitrogen-containing bases are C₁-C₆-alkylamines,preferably trialkylamines, for example triethylamine, trimethylamine,N-ethyldiisopropylamine, ammonia, N-methylpiperidine, pyridine,substituted pyridines such as lutidine, collidine and4-(dimethylamino)pyridine (DMAP), N-methylmorpholine, imidazole,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

Preferred bases are tertiary amines and alkali metal and alkaline earthmetal carbonates and bicarbonates as mentioned above.

Especially preferred bases are triethylamine and alkali metal andalkaline earth metal carbonates as mentioned above.

The term base as used herein also includes mixtures of two or more,preferably two of the above compounds. Particular preference is given tothe use of one base.

The bases are generally employed in equimolar amounts; however they canalso be employed in catalytic amounts, in excess or, if appropriate, beused as solvent.

In another embodiment the reaction of the amino-benzoxazinone of formula(VIII) with the compounds of formula (IX) is carried out in the absenceof a base. Such embodiment is preferred.

The reaction may in principle be carried out in substance. However,preference is given to reacting the amino-benzoxazinones (VIII) with thecompounds of formula (IX), and optionally a base, in an organic solvent.Suitable in principle are all solvents which are capable of dissolvingthe amino-benzoxazinones (VIII) and the compounds of formula (IX), andoptionally a base at least partly and preferably fully under reactionconditions.

Examples of suitable solvents are aliphatic hydrocarbons such aspentane, hexane, cyclohexane, nitromethane and mixtures ofC₅-C₈-alkanes; aromatic hydrocarbons such as benzene, chlorobenzene,toluene, cresols, o-, m- and p-xylene; halogenated hydrocarbons such asdichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachlorideand chlorobenzene; ethers such as diethyl ether, diisopropyl ether,tert.-butyl methylether (TBME), dioxane, anisole and tetrahydrofuran(THF); esters such as ethyl acetate and butyl acetate; nitriles such asacetonitrile and propionitrile; ketones such as acetone, methyl ethylketone, diethyl ketone, tert-butyl methyl ketone, cyclohexanone; as wellas dipolar aprotic solvents such as sulfolane, dimethyl-sulfoxide,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),1,3-dimethyl-2-imidazolidinone (DMI), N,N′-dimethylpropylene urea(DMPU), dimethyl sulfoxide (DMSO) and 1-methyl-2 pyrrolidinone (NMP).

Preferred solvents are ethers, esters, aromatic hydrocarbons andnitriles as described above. Particularly preferred solvents are THF,ethyl acetate, toluene and acetonitrile.

Especially preferred solvents are ethyl acetate and toluene.

The term solvent as used herein also includes mixtures of two or more ofthe above solvents.

For the reaction, the amino-benzoxazinones of formula (VIII), thecompounds of formula (IX) and optionally the base may be contacted withone another in any desired manner, i.e. the reactants and optionally thebase may be introduced into the reaction vessel separately,simultaneously or successively and reacted. For example, theamino-benzoxazinones of formula (VIII) and the compounds of formula (IX)may be initially charged in a reaction vessel, if appropriate with thedesired solvent, and then the desired reaction conditions may beattained. However, it is also possible to introduce the majority orentirety of the amino-benzoxazinones of formula (VIII) and subsequentlyadd the compounds of formula (IX), if appropriate in a solvent, underreaction conditions, into the reaction vessel.

In one embodiment of the process according to the invention, thecompounds of formula (IX) and optionally the base are initially chargedin a reaction vessel, if appropriate with the desired solvent, andsubsequently the amino-benzoxazinones of formula (VIII) are added, morepreferably are added a little at a time, into the reaction vessel.

In another embodiment of the process according to the invention, theamino-benzoxazinones of formula (VIII) and optionally the base areinitially charged in a reaction vessel, if appropriate with the desiredsolvent, and subsequently the compounds of formula (IX) are added, morepreferably are added a little at a time, into the reaction vessel. Suchembodiment is preferred.

In a further preferred embodiment of the invention, the majority, inparticular at least 80% and more preferably the entirety or virtuallythe entirety (>95%) of the amino-benzoxazinones of formula (VIII) andoptionally the base are initially charged, and the majority, inparticular at least 80% and more preferably the entirety or virtuallythe entirety (>95%) of the compounds of formula (IX) is added theretounder reaction conditions in the course of the reaction, for exampleover a period of from 0.5 to 20 h and in particular from 1 to 10 h. Tothis end, the compounds of formula (IX) will preferably be dissolved ina solvent.

The reaction can be carried out at atmospheric pressure, reducedpressure or under elevated pressure, if appropriate under an inert gas,continuously or batchwise.

It might be advantageous to partly, almost completely or completelyremove the HCl formed in the course of the reaction.

After completion or partial completion of the reaction, the reactionmixture can be worked up by the methods customary for the purpose bymeans of standard techniques. Examples thereof include filtration,aqueous work-up, and evaporation of solvents and/or other volatilecompounds. These methods can also be combined with each other.

In general the solvent used is removed by customary methods,distillatively for example. The crude product can then be taken up in anon-water-miscible organic solvent, any impurities extracted withunacidified or acidified water, and the system can then be dried and thesolvent removed under reduced pressure.

In case the reaction of the amino-benzoxazinones of formula (VIII) withcompounds of formula (IX), is conducted in the absence of a base,preferably the solvent and optionally the excess of compounds of formula(IX) are removed by customary methods, e.g. by distillation.

Another option for work-up is to remove the HCl developed during thereaction in vacuo or by means of an inert gas flow, and then used thesolution obtained without further purification in the subsequentreaction.

In case the reaction of the amino-benzoxazinones of formula (VIII) withcompounds of formula (IX) is conducted in the presence of a base, afterthe ending of the reaction, preferably in a further step the reactionmixture is diluted by addition of water followed by phase separation.The solvent can then be removed by customary methods.

Generally the product is obtained with high purity. If necessary, forfurther purification it is possible to employ the typical methods suchas crystallization, precipitation (for example by addition of an apolarsolvent such as pentane, cyclohexane, heptane or toluene, or mixtures ofsaid solvents) or chromatography.

The invention is illustrated by the following examples without beinglimited thereto or thereby.

EXAMPLES

The yields of the carbamates of formula (I), the carbamat-benzoxazinonesof formula (VI), and the benzoxazinones of formula (VIII) were, unlessstated otherwise, determined by means of quantitative HPLC:

Method A

Sample preparation:

-   -   The samples of the products to be determined were weighed into a        100 ml standard flask which was made up to 100 ml with        acetonitrile.        Chromatographic conditions:    -   Column: Zorbax Eclipse XDB-C18 1.8 μm 50×4.6 mm from Agilent®    -   Wavelength: 210 nm    -   Eluent: gradient of A (0.1% by volume of H₃PO₄ in H₂O) and B        (0.1% by volume of H₃PO₄ in acetonitrile); starting with 2% B,        then B rising from 2% to 30% within 2 min, then B rising from        30% to 100% within 6 min, then 2 min 100% B, then back to 2%        within 0.1 min.    -   Flow rate: 1.4 ml/min    -   Pressure: approx. 210 bar

Calibration:

The calibration was effected with external standard. To establish thestandard, a total of 5 samples of the pure substances were weighed inthe following concentrations (preci-sion+/−0.1 mg): approx. 0.02 g/I,approx. 0.04 g/I, approx. 0.06 g/I, approx. 0.08 g/I, approx. 0.10 g/I.With the aid of a suitable PC program, a calibration line wasestablished. For the substances detailed above, this was a linearfunction. Standard deviation, correlation coefficient and straight-lineequation were calculated. For each of the components, theirconcentration can thus be determined based on the particular externalstandard.

Method B

Sample preparation:

-   -   The samples of the products to be determined were weighed into a        100 ml standard flask which was made up to 100 ml with        acetonitril.        Chromatographic conditions:    -   Column: Zorbax SB-Phenyl 1.8 μm 50×4.6 mm from Agilent®    -   Wavelength: 210 nm    -   Eluent: gradient of A (0.1% by volume of H₃PO₄ in H₂O) and B        (acetonitrile); starting with 15% B, then B rising from 15% to        50% within 5 min, then B rising from 50% to 100% within 5 min,        then 2 min 100% B, then back to 15% within 0.1 min.    -   Flow rate: 1.3 ml/min    -   Pressure: approx. 365 bar

Calibration:

-   -   The calibration was effected with external standard. To        establish the standard, a total of 5 samples of the pure        substances were weighed in the following concentrations        (preci-sion+1-0.1 mg): approx. 0.01 WI, approx. 0.05 WI, approx.        0.10 WI, approx. 0.15 WI, approx. 0.20 WI. With the aid of a        suitable PC program, a calibration line was established. For the        substances detailed above, this was a linear function. Standard        deviation, correlation coefficient and straight-line equation        were calculated. For each of the components, their concentration        can thus be determined based on the particular external        standard.

1. Preparation of carbamates of formula (I) Example 1.1 MethylN-methyl-N-(methylcarbamothioyl)carbamate

420.9 g (4.00 mol) N,N-dimethylthiourea with a purity of 99% werecharged to 2000 g toluene. 507 g (4.78 mol) sodium carbonate was addedand the suspension heated to 65° C. Afterwards 432.2 g (4.60 mol) methylchloroformate were dosed in over 5 h at 65° C. The mixture waspoststirred at the same temperature over 0.5 h. For work up,demineralized water was added under agitation and the phases separated.The aqueous phase was extracted with 800 g toluene and the organicphases were combined. The product content of the organic solution wasdetermined with 15.15% by quant. HPLC (HPLC-method A; t_(R)=3.6 min),which corresponds to a chemical yield of 90.3%.

¹H-NMR (CDCl₃, 400 MHz): 10.1-10.3 (1H, s), 3.82 (3H, s), 3.66 (3H, s),3.17 (3H, d).

Examples 1.2 and 1.3 Phenyl N-methyl-N-(methylcarbamothioyl)carbamate

Example 1.2

N,N′-dimethyl thiourea of example 2.1 (0.66 mol) was dissolved in ethylacetate. 106.0 g (1.00 mol) sodium carbonate were added and 156.6 g(1.00 mol) phenyl chloroformate were dosed over a period of 30 min withthe temperature rising to 63° C. The mixture was poststirred at 66° C.for 0.5 h. Demineralized water was added under agitation at the sametemperature and the phases separated. A vacuum was applied to theorganic phase and 200 ml of a two-phase liquid were distilled off. Thevessel was cooled to 5° C. and stirred for 1 h at this temperature. Theproduct was collected by filtration and washed once with cyclohexane.The resulting solid was dried to yield 114.0 g (0.50 mol) of colourlesscrystals with a purity of 98% (HPLC-method B; t_(R)=5.93 min) and amelting point of 133-135° C. (corresponding chemical yield: 75%).

¹H-NMR (CDCl₃, 400 MHz): 10.5-10.6 (1H, s), 7.38-7.46 (2H, m), 7.24-7.32(1H, m), 7.09-7.17 (2H, m), 3.89 (3H, s), 3.17 (3H, d).

Example 1.3

50.0 g (0.66 mol) methylisothiocyanate with a purity of 98% were addedto ethyl acetate. 22.0 g (0.71 mol) of methyl amine were introduced at20-30° C. with a dip tube. Nitrogen was bubbled through the solution for14 h. 106.0 g (1.00 mol) sodium carbonate were added and 156.6 g (1.00mol) phenyl chloroformate were dosed over a period of 30 min with thetemperature rising from 30° C. to 60° C. The mixture was poststirred at70° C. for 0.5 h. Demineralized water was added under agitation at thesame temperature and the phases separated. A vacuum was applied to theorganic phase and 100 ml of a two-phase liquid were distilled off. Thevessel was cooled to 5° C. and stirred for 1 h at this temperature. Theproduct was collected by filtration and washed once with 50 g ofcyclohexane. The resulting solid was dried to yield 124.0 g (0.54 mol)of colourless crystals with a purity of 98% (HPLC-method B; t_(R)=5.93min; corresponding chemical yield: 82.1%).

2. Preparation of precursors and intermediates for the carbamates offormula (I) Example 2.1 N,N′-dimethyl thiourea

50.0 g (0.66 mol) methylisothiocyanate with a purity of 97% were addedto xylene (isomeric mixture). 20.6 g (0.66 mol) of methyl amine wereintroduced at 20-30° C. with a dip tube resulting in the formation oftwo layers. The lower slightly yellow layer was separated, transferredto a rotary evaporator, and treated with a vacuum of 10 mbar at 50° C.for 30 min. Qualitative analytics (HPLC, GC) showed complete conversionto N,N′-dimethyl thiourea (no MITC detectable), the composition was 88%DMTU and 12% xylene (GC-area-%).

3. Preparation of carbamat-benzoxazinones of formula (VI) Examples 3.1to 3.5 PhenylN-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-1,4-benzoxazin-6-yl)carbamate

Example 3.1

182.9 g (0.700 mol)6-Amino-2,2,7-trifluoro-4-prop-2-ynyl-4H-benzo[1,4]oxazin-3-one with apurity of 98.1% were dissolved in 521.1 g toluene and heated to reflux(110° C.) under agitation. 122.1 g (0.780 mol) phenyl chloroformate wereadded over 1 h at 107-112° C. (reflux) and the mixture afterwardspoststirred over 1 h at the same temperature (HCl offgas). Low boilerswere removed with a rotary evaporator under vacuum. 281.3 g (0.707 mol)of the product were obtained with 94.6% purity determined byquantitative HPLC method A (t_(R)=5.7 min; corresponding chemical yield100%).

1H-NMR (500 MHz, CDCl₃): δ (ppm)=2.31 (t, 1H), 4.76 (d, 2H), 7.07 (d,1H), 7.19-7.31 (m, 4H), 7.43 (t, 2H), 8.28 (d, 1H).

Example 3.2

53.2 g (0.200 mol)6-Amino-2,2,7-trifluoro-4-prop-2-ynyl-4H-benzo[1,4]oxazin-3-one with apurity of 96.3% were dissolved in 500 mL acetonitrile. 18.48 g (0.22mol) sodium bicarbonate were added. 34.4 g (0.22 mol) phenylchloroformate were added slowly at 22° C. and the temperature was keptconstant by an ice bath. The mixture was stirred for 3 h at roomtemperature. The solids were removed by filtration. 500 mLdichloromethane were added to the solution and the organic phase waswashed three times with water. The organic phase was dried over MgSO₄and evaporated to dryness. The residue was triturated with warmcyclohexane. The residue was removed by filtration and washed withcyclohexane. 74.0 g of the product were obtained as off-white solid,with a purity of 96.3% determined by quantitative HPLC method A(t_(R)=5.7 min), which corresponds to a chemical yield of 94.7%.

Example 3.3

1.5 g (5.8 mmol)6-Amino-2,2,7-trifluoro-4-prop-2-ynyl-4H-benzo[1,4]oxazin-3-one with apurity of 98.4% were dissolved in 6 g THF. 0.95 g (6.1 mmol) phenylchloroformate were added. A temperature rise from 23° C. to 32° C. wasobserved. The mixture was stirred for 1 h at room temperature. Themixture was evaporated to dryness. 2.2 g of the product with a purity of96.2% determined by quantitative HPLC method A (t_(R)=5.7 min) wereobtained, which corresponds to a chemical yield 97%.

Example 3.4

6.5 g (24.9 mmol)6-Amino-2,2,7-trifluoro-4-prop-2-ynyl-4H-benzo[1,4]oxazin-3-one with apurity of 98.1% were dissolved in 18.8 g ethyl acetate. The solution washeated to 77° C. and 4.3 g (27.5 mmol) phenyl chloroformate were addedwithin 30 min. The mixture was stirred for 1 h at 77° C. and evaporatedto dryness. 9.95 g of the product with a purity of 94.6% determined byquantitative HPLC method A (t_(R)=5.7 min) were obtained, whichcorresponds to a chemical yield of 100%.

Example 3.5

In a nitrogen inerted, stirred reactor 119.8 g of dry ethyl acetate(100%) and 119.8 g (0.758 mol) of phenyl chloroformate (99%) wasprecharged and heated up to 85° C. (reflux conditions). 868.8 g (0.702mol) of a 20.7% solution of6-Amino-2,2,7-trifluoro-4-prop-2-ynyl-4H-benzo[1,4]oxazin-3-one in ethylacetate was preheated to 60° C. and dosed over 2.5 h. During the dosageHCl gas was formed as co-product and sent to a scrubber operated withNaOH (10%). After a post reaction time of 0.5 h at 79° C. (refluxconditions), 634 g of the solvent was distilled off at normal pressure.Subsequently 698 g of fresh ethyl acetate (100%) was added and 647 gdistilled off again. 876.9 g of dry DMF (100%) was added and 280.8 g ofsolvent (mainly ethyl acetate) was distilled off at 120-10 mbar andinternal temperatures up to 50° C. 1112.0 g of a DMF solution containing23.4% of the product determined by quantitative HPLC method B (t_(R)=6.9min) was obtained, corresponding to 98.5% chemical yield.

4. Preparation of the Benzoxazinones of Formula (VII) Examples 4.1 to4.71,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione

Example 4.1

4.49 g (20.0 mmol) phenyl N-methyl-N-(methylcarbamothioyl)carbamate and7.84 g (20.0 mmol) phenylN-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]carbamate(purity 96%) were dissolved in 40 mL N,N-dimethylformamide (DMF), 0.33 g(4.0 mmol) sodium acetate were added and the mixture heated to 60° C.After 3.5 h 32 ml DMF were removed by distillation at 50° C. underreduced pressure. The product precipitated after addition of a mixtureof 25 mL methanol and 25 mL H₂O. The solids were collected and washedwith 10 mL water and 10 mL methanol. 7.8 g (purity by quant. HPLC 97.8wt % corresponding to 93% chemical yield; HPLC-method A; t_(R)=5.9 min)of the title compound were obtained.

¹H-NMR (CDCl₃, 400 MHz): 7.27 (1H, d), 7.18 (1H, d), 4.76 (2H, s), 3.80(6H, s), 2.38 (1H, s)

Example 4.2

0.56 g (2.5 mmol) phenyl N-methyl-N-(methylcarbamothioyl)carbamate and0.98 g (2.5 mmol) phenylN-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]carbamate(purity 96%) were dissolved in 20 mL tetrahydrofuran (THF). 49 mg (0.50mmol) potassium acetate were added and the mixture heated to 60° C.After 4 h the solvent was removed. The product solidified after additionof 10 g 60% aqueous methanol. The solids were collected and washed twicewith 2 mL 60% aqueous methanol. 0.95 g (purity by quant. HPLC 99.5 wt %corresponding to 92% chemical yield; HPLC-method A; t_(R)=5.9 min) ofthe title compound were obtained.

Example 4.3

1.03 g (4.02 mmol)6-amino-2,2,7-trifluoro-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-3-onewas dissolved in 20 mL THF. A solution of 0.63 g (4.02 mmol) phenylchloroformate in THF was added at 55° C. The mixture was stirred for 30min at this temperature. Formed HCl was stripped by a nitrogen stream. 8mL DMF were added and THF distilled off under vacuum. 65 mg (0.79 mmol)sodium acetate and 0.97 g (4.02 mmol) phenylN-methyl-N-(methylcarbamothioyl)carbamate (purity 93%) was added and themixture stirred at 45° C. until HPLC showed complete conversion. 6 g DMFwas removed by distillation under reduced pressure and the productprecipitated after addition of 8 g 60% aqueous methanol. The solids werecollected, washed twice with 60% aqueous methanol and dried in vacuum.1.51 g (purity by quant. HPLC 97.3% corresponding to 97% chemical yield;HPLC-method A; t_(R)=5.9 min) of the title compound were obtained.

Example 4.4

3.24 g (20.0 mmol) methyl N-methyl-N-(methylcarbamothioyl)carbamate weredissolved in 30 g DMF and 0.21 g (2.0 mmol) Na₂CO₃ was added. Thepressure was reduced to 12 mbar and the mixture heated to reflux (40-42°C.). 7.96 g (20.0 mmol) phenylN-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]carbamate(purity 94.5%) in 20 g DMF were added continuously over 60 min. Methanolformed in the course of the reaction was removed by co-distillation withDMF. The solvent volume was kept constant by addition of pure DMF from asecond feed vessel. The mixture was stirred for another 30 min at thistemperature and for 90 min at 25° C. The resulting solution (39.5 g)contained 20.2 wt % of the title compound corresponding to 96.5%chemical yield (HPLC-method A; t_(R)=5.9 min)

Example 4.5

In a nitrogen inerted, stirred reactor 118.7 g of dry ethyl acetate(100%) and 59.3 g (0.375 mol) of phenylchloroformate (99%) wereprecharged and heated up to 85° C. (reflux conditions). A solution of100 g (0.354 mol) of6-amino-2,2,7-trifluoro-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-3-one(90.7%) in 400 g of ethyl acetate was preheated to 60° C. and dosed over2.5 h. During the dosage HCl gas was formed as co-product and sent to ascrubber operated with NaOH (10%). After a post reaction time of 0.5 hat 79° C. (reflux conditions), 400 g of the solvent was distilled off atnormal pressure. Subsequently 400 g of fresh ethyl acetate was added anddistilled off again. 441.4 g of DMF was added and 162.8 g of solvent(mainly ethyl acetate) was distilled off at 120-10 mbar and internaltemperatures up to 50° C. At 50° C. 80.1 g (0.350 mol) of phenylN-methyl-N-(methylcarbamothioyl)carbamate (98.1%) was added followed by5.8 g (0.071 mol) of dry sodium acetate (100%). The mixture was stirred3.5 h at 50° C. Afterwards 258.0 g of DMF was distilled off at 5-10 mbarand internal temperatures up to 55° C. For precipitation of the titlecompound 601.8 g of a mixture methanol/water 3:2 was precharged in asecond reactor and heated up to 50° C.

At 50° C. 1.8 g (0.0044 mol) of1,5-dimethyl-6-thioxo-3-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]-1,3,5-triazinane-2,4-dionewas added. Then the concentrated DMF solution of the raw product wasdosed in 1.5 h at 50° C. Afterwards the mixture was cooled down to 10°C. and stirred 0.5 h at 10° C. The precipitated product was isolated byfiltration and washed twice with 150 g of a mixture methanol/water 3:2precooled to 0° C. The wet filter cake was dried in a vacuum dryingoven. 134.9 g (0.315 mol) of the title compound (96.3 wt % puritydetermined by quant. HPLC (HPLC-method B; t_(R)=7.1 min) were obtained(corresponding to 89% chemical yield).

Example 4.6

44 g (0.27 mol) methyl N-methyl-N-(methylcarbamothioyl)carbamate, purity94.1%, in 414 g DMF were charged to a laboratory glass vessel. 4.64 g(44 mmol) Na₂CO₃ was added. The mixture was heated to reflux at 10mbar/40° C. Afterwards 111 g (0.27 mol) phenylN-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]carbamate(purity 91.6%) in 372 g DMF was dosed in at 40° C. under reflux of DMFover 4 h (40° C., 10 mbar). The generated methanol was not condensedtogether with the DMF and so removed from the mixture. Afterpoststirring of 30 min, the major part of DMF was distilled off (10-20mbar, 50° C.). The vessel content was cooled to 20° C. and a mixture of487 g MeOH and 487 g demineralized water was added for precipitation.The resulting suspension was cooled to 3° C. and the product wasfiltered, washed with water and dried in a vacuum cabinet at 50° C.

107 g (0.255 mol) of the product with a purity of 98.4% determined byquant. HPLC (HPLC-method A; t_(R)=5.9 min) have been obtained(corresponding to 94.5% chemical yield).

Example 4.7

0.38 g (2.0 mmol) ethyl N-methyl-N-(methylcarbamothioyl)carbamate with apurity of 91.9% was added to 3.5 g DMF. Under agitation, 0.76 g (2.0mmol) phenylN-[2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]carbamate(98.5% purity) and 0.01 g (0.14 mmol) of NaOH powder were added at 35°C. After a poststirring period of 2 h, a chemical yield 70.1% wasdetermined by quantitative HPLC analytics (HPLC-method A; t_(R)=5.9 min)of the product solution.

Example 4.81,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl]-1,3,5-triazinane-2,4-dione

0.97 g (5.0 mmol) methyl N-methyl-N-(methylcarbamothioyl)carbamate witha purity of 83.3% was dissolved in 4.2 g DMF. 0.14 g (1.7 mmol) sodiumacetate was added. The mixture was stirred at 60° C. at a pressure of 25mbar. Via syringe a solution of 1.32 g (3.7 mmol) phenylN-(2,2,7-trifluoro-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl)carbamate(purity 95.7%) in 4.2 g DMF was added within 2 h. From time to timefresh DMF was added to maintain the solvent volume. After a poststirringperiod of 1 h, a chemical yield 73% was determined by quantitative HPLCanalytics (HPLC-method A; t_(R)=4.9 min) of the product solution.

¹H-NMR (DMSO-d₆, 400 MHz): 11.98 (1H, br), 10.07 (1H, br), 7.54 (1H, d),7.40-7.49 (3H, m), 7.20-7.30 (3H, m).

1-7. (canceled)
 8. A compound of formula (I),

wherein R¹ is H or C₁-C₆-alkyl; R² is methyl; R³ is C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-cyanoalkyl, C₁-C₆-nitroalkyl, aryl, 5- or6-membered heteroaryl or aryl-C₁-C₆-alkyl, wherein the aryl orheteroaryl rings are unsubstituted, partially or fully halogenated, orsubstituted by one to five substituents selected from the groupconsisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, formyl, C₁-C₆-alkylcarbonyl, hydroxycarbonyl, andC₁-C₆-alkoxycarbonyl; and Z is S.
 9. The compound of claim 8, wherein R³is C₁-C₆-alkyl or aryl, wherein the aryl ring is unsubstituted orsubstituted by one halogen atom or one C₁-C₆-alkyl group.
 10. Thecompound of claims 8, wherein R¹ is C₁-C₆-alkyl.
 11. The compound ofclaim 8, wherein R¹ is methyl.
 12. The compound of claim 8, wherein R¹and R³ are both methyl.
 13. The compound of claim 8, wherein R¹ ismethyl and R³ is phenyl.
 14. A process for the preparation of thecompound of formula (I) as claimed in claim 8 wherein a compound offormula (II),

is reacted with the compound of formula (III)

in the presence of a base.
 15. A process for preparing a compound offormula (II) comprising a) reacting a compound UI formula (IV)Z═C═N—R¹  (Iv) wherein R¹ is H or C₁-C₆-alkyl; and Z is S. With acompound of formula (V)H₂N—R²  (V) wherein R² is methyl.
 16. The process as claimed in claim15, wherein the compound of formula (II) is not isolated, and thereaction mixture obtained in step a) is directly used in the reaction togive carbamates of formula (I).
 17. A method for preparing a compound offormula (VII)

wherein R¹, R² and Z are as defined in claim 8; R⁴ is H, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-alkenyl, C₃-C₆-haloalkenyl,C₃-C₆-alkynyl, C₃-C₆-haloalkynyl, C₁-C₆-alkoxy orC₃-C₆-cycloalkyl-C₁-C₆-alkyl; R⁵ is H, halogen or C₁-C₆-alkyl; R⁶ is H,halogen or C₁-C₆-alkyl; R⁷ is H, halogen or C₁-C₆-alkyl; and W is O orS; comprising reacting the compound of claim 8 with a compound offormula (VI)

wherein R⁴ is H, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-alkenyl, C₃-C₆-haloalkenyl, C₃-C₆-alkynyl, C₃-C₆-haloalkynyl,C₁-C₆-alkoxy or C₃-C₆-cycloalkyl-C₁-C₆-alkyl; R⁵ is H, halogen orC₁-C₆-alkyl; R⁶ is H, halogen or C₁-C₆-alkyl; R⁷ is H, halogen orC₁-C₆-alkyl; R⁸ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-cyanoalkyl,C₁-C₆-nitroalkyl, aryl, 5- or 6-membered heteroaryl or aryl-C₁-C₆-alkyl,wherein the aryl or heteroaryl rings are unsubstituted, partially orfully halogenated, or substituted by one to five substituents selectedfrom the group consisting of CN, NO₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, OH,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, formyl, C₁-C₆-alkylcarbonyl,hydroxycarbonyl, and C₁-C₆-alkoxycarbonyl; and W is O or S; in thepresence of a base.